CN113433752A - Preparation method of fast response electrochromic device based on PMMA/PVDF-HFP gel electrolyte - Google Patents
Preparation method of fast response electrochromic device based on PMMA/PVDF-HFP gel electrolyte Download PDFInfo
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Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1506—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
- G02F1/1508—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode using a solid electrolyte
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect the electrolyte is made of polymers
Abstract
The invention discloses a preparation method of a PMMA/PVDF-HFP gel electrolyte-based fast response electrochromic device, and relates to the field of electrochromism. The electrochromic device comprises a working electrode, a counter electrode and an electrolyte layer, wherein the working electrode is a nano inclined columnar WO deposited on ITO transparent conductive glass3‑xA film; the counter electrode is nano inclined columnar Ni deposited on ITO transparent conductive glassxOyA film; and the PMMA/PVDF-HFP gel electrolyte layer is positioned between the working electrode and the counter electrode, and the electrochromic device is encapsulated by using ultraviolet curing glue. The solid film type electrochromic device is not easy to leak and has a rapid response characteristic, the coloring response time is 6-8s, and the fading response time is 7-10 s.
Description
Technical Field
The invention relates to the technical field of electrochromic devices, in particular to a method for preparing a nano inclined columnar structure WO by utilizing a glancing angle direct current magnetron sputtering technology3-xAnd NixOyThe thin film respectively serves as an electrochromic layer and an ion storage layer. The preparation method of the electrochromic device based on the polymethyl methacrylate/polyvinylidene fluoride-hexafluoropropylene gel electrolyte layer solves the problems that the film nano structure is difficult to control in the existing electrochromic device and liquid leakage exists in the liquid electrolyte electrochromic device.
Background
The electrochromic principle is that electrochromic material and electrolyte are assembled together and clamped between transparent conducting layers, and reversible change of color is realized by applying a certain driving voltage externally. Applying a forward voltage, and injecting ions and electrons from the electrolyte layer into the electrochromic layer to realize color generation; conversely, when a reverse voltage is applied, ions and electrons are extracted from the electrochromic layer to effect color fading.
The liquid electrolyte has good ionic conductivity, and is the earliest studied electrolyte type. The fatal defects of difficult encapsulation and easy liquid leakage are gradually eliminated. Solid polymer electrolytes have the following advantages over liquid electrolytes: the electrode surfaces in the solid polymer electrolyte are free of internal shorts, electrolyte leakage and non-combustible reaction products. Although the ionic conductivity is relatively low, the electrolyte is simple to manufacture, safe, good in mechanical property and easy to realize large-scale production, and is the most studied electrolyte type. The gel electrolyte called as the third generation polymer electrolyte is prepared by adding polymer into liquid non-proton electrolyte, which is between liquid state and solid state, the gel has solid viscosity and liquid diffusivity, and has better light transmittance and higher safety than liquid state.
Polymethyl methacrylate (PMMA) is a transparent amorphous polymer, Li+The complexation with the polymer host and the lithium salt determines the size of the electrochemical stability window. The gel-state polymer electrolyte taking PMMA as a matrix material has excellent interface stability, and the PMMA has the advantages of abundant raw materials, low price, simple preparation, no toxicity and no fluorine. In an electrolyte system taking PMMA as a matrix, a carbonyl side group exists in a Methyl Methacrylate (MMA) unit, and the carbonyl side group has strong interaction with an oxygen atom in a carbonate plasticizer, so that the PMMA-based electrolyte system can contain a large amount of liquid electrolyte and shows good compatibility. Better electrolyte absorption allows PMMA to exhibit higher ionic conductivity.
Disclosure of Invention
A preparation method of a PMMA/PVDF-HFP gel electrolyte based fast response electrochromic device solves the problems that a liquid electrolyte is difficult to package and easy to leak in the electrochromic device, simplifies the assembly process of the electrochromic device, and has good electrochromic performance.
A method for preparing a fast response electrochromic device based on PMMA/PVDF-HFP gel electrolyte comprises the steps of preparing the device, and forming the device by an electrolyte, a working electrode and a counter electrode.
The electrolyte is prepared by taking polymethyl methacrylate (PMMA) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) as matrixes and adopting a solvent evaporation method: the content of polymethyl methacrylate/polyvinylidene fluoride-hexafluoropropylene (PMMA/PVDF-HFP) is 10wt%, and the mass ratio of polymethyl methacrylate (PMMA) to polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) is 9: 1-6: 4.
The polymethyl methacrylate (PMMA) is used for heat-resistant optics, and the molecular weight is 30-60 ten thousand.
The conductive glass substrate is ITO transparent conductive glass.
The invention provides a preparation method of an electrochromic device, which comprises the following steps:
（1）WO3-xfilm and NixOyThe films are prepared by glancing angle direct current magnetron sputtering;
(2) anhydrous lithium perchlorate (LiClO)4) Dissolving the mixed solution of propylene carbonate and acetonitrile, and stirring to obtain a transparent and uniform mixed electrolyte solution;
(3) adding polymethyl methacrylate/polyvinylidene fluoride-hexafluoropropylene (PMMA/PVDF-HFP) into the electrolyte solution obtained in the step (2), and stirring to obtain a uniform mixed solution, wherein the content of the polymethyl methacrylate/polyvinylidene fluoride-hexafluoropropylene (PMMA/PVDF-HFP) is 10 wt%;
(4) will deposit NixOyPutting the film into a container with the surface facing upwards, pouring the mixed solution prepared in the step (3), and performing vacuum drying to ensure that the electrolyte is tightly combined and deposited with NixOyA thin film of conductive glass;
(5) will deposit WO3-xConductive glass of film and Ni deposition in step (4)xOyAnd (3) alternately laminating the conductive glass of the film, carrying out vacuum drying at the temperature of 60-90 ℃ for 1-2 h, and packaging to obtain the electrochromic device (ECD).
The step (1) NixOyThe film preparation process parameters are as follows: the deposition temperature is 150 ℃, and the deposition pressure is 7.5 multiplied by 10- 1pa, sputtering power of 100W, deposition time of 40 min.
Said step (1) WO3-xThe film preparation process parameters are as follows: the deposition temperature is 150 ℃, and the deposition pressure is 5 multiplied by 10-1pa, sputtering power of 200W, deposition time of 1 h.
Said step (1) WO3-xThe film has a nano inclined columnar structure and is tightly combined with the ITO film.
The step (1) NixOyThe film has a nano inclined columnar structure and is tightly combined with the ITO film.
The stirring temperature of the electrolyte solution in the step (2) is 25 ℃.
The mass ratio of the polymethyl methacrylate/the polyvinylidene fluoride-hexafluoropropylene (PMMA/PVDF-HFP) in the step (3) is 9: 1-6: 4; the molecular weight of PMMA is 30-60 ten thousand.
And (3) stirring the solution in the step (3) at the temperature of 65-75 ℃ for 2.5-3.5 h.
And (3) stirring the electrolyte solution in the step (4) at the temperature of 60-90 ℃, and drying for 8-10 h in vacuum.
The packaging method in the step (5) is vacuum ultraviolet curing packaging.
The invention prepares a fast response thin film type electrochromic device based on a gel electrolyte.
The preparation method of the PMMA/PVDF-HFP gel electrolyte based fast response electrochromic device overcomes the defects of difficult assembly, easy leakage and the like of a liquid electrolyte, simplifies the assembly process of the electrochromic device and is easy to industrialize; an electrochromic layer and an ion storage layer of a PMMA/PVDF-HFP gel electrolyte based fast response electrochromic device have a nano inclined column structure, can provide a channel for injecting/extracting reactive ions and electrons, and show a fast response characteristic.
Drawings
FIG. 1 is WO3-xSEM image of the film.
FIG. 2 shows NixOySEM image of the film.
Fig. 3 is a schematic structural diagram of a PMMA/PVDF-HFP gel electrolyte-based fast response electrochromic device.
FIG. 4 shows ITO/WO at a wavelength of 800nm under a driving voltage of + -5V3-x/PMMA/PVDF-HFP/NixOyOptical modulation amplitude of ITO electrochromic device.
FIG. 5 shows ITO/WO3-x/PMMA/PVDF-HFP/NixOyResponse time of ITO electrochromic device.
FIG. 6 shows ITO/WO3-x/PMMA/PVDF-HFP/NixOyA real object diagram of the ITO electrochromic device.
Detailed Description
In order to make the technical scheme of the invention clearer, the following description will explain the invention in detail through specific implementation cases.
Embodiment 1
The advantages of this embodiment:
1. the embodiment relates to a preparation method of a PMMA/PVDF-HFP gel electrolyte-based fast response electrochromic device, and the light modulation amplitude of the device prepared by the method at 800nm is 31.6 percent;
2. the preparation method of the PMMA/PVDF-HFP gel electrolyte-based fast response electrochromic device has the advantages that the response time of the prepared device is short, the color response time is 7-10s, and the color fading response time is 8-10 s;
3. the transmittance of the PMMA/PVDF-HFP electrolyte prepared by the embodiment is 86.11%;
4. this embodiment prepares a transparent electrolyte film and an electrochromic film; mixing transparent nanometer inclined column shaped WO3-xElectrochromic film as working electrode, transparent nano inclined columnar NixOyThe ion storage film is used as a counter electrode, the device has the advantages of quick response and high contrast, the defects of difficult packaging and complex preparation process of the electrochromic device are overcome, convenience is provided for industrial production, and the application field of the electrochromic device is expanded.
The embodiment can obtain the preparation method of the quick response electrochromic device based on the PMMA/PVDF-HFP gel electrolyte.
This embodiment mode will explain the electrochromic layer and the ion storage layer in detail.
1. This embodiment WO3-xAnd NixOyThe film preparation all adopts a glancing angle direct current magnetron sputtering system. The magnetron sputtering system is a vacuum device and consists of a vacuum cavity comprising a sputtering target material, a workpiece table, a transmission mechanism and a rotating mechanism, wherein the transmission mechanism consists of a driving motor, a driving shaft and a gear transmission device, and the rotating mechanism consists of an index plate, a magnetic rotating device and a workpiece table supporting device.
2. This embodiment WO3-xAnd NixOyThe preparation method of the film comprises the following steps:
(1) sequentially ultrasonically cleaning an ITO conductive glass substrate in acetone and absolute ethyl alcohol for 15-20 min respectively, and drying at 50-60 ℃ for 1-2 h to obtain a clean glass substrate;
（2）WO3-xpreparing a film: WO with the thickness of 420-450 nm is deposited on the surface of the clean ITO conductive glass by adopting a glancing angle magnetron sputtering method3-xFilm to obtain WO with nano inclined column-shaped surface3-xA thin film of conductive glass;
（3）NixOypreparing a film: depositing Ni with the thickness of 420-450 nm on the surface of the clean ITO conductive glass by adopting a glancing angle magnetron sputtering methodxOyFilm to obtain Ni plated with nanometer inclined column on surfacexOyThin film conductive glass.
The parameters of the magnetron sputtering coating shown in the step (2) are specifically as follows: the target material is a metal W target, the sputtering power supply is a direct current power supply, the target base distance is 10 cm, and the glancing angle is 80oThe bulk vacuum degree is 4 multiplied by 10-3pa working gas flow of 27sccm argon, reaction gas flow of 16sccm oxygen, deposition temperature of 150 ℃ and deposition pressure of 5 × 10-1pa, the sputtering power is 200W, and the deposition time is 0.5-1.5 h.
The parameters of the magnetron sputtering coating shown in the step (3) are specifically as follows: the target material is a metal Ni target, the sputtering power supply is a direct current power supply, the target base distance is 10 cm, and the glancing angle is80oThe bulk vacuum degree is 4 multiplied by 10-3pa working gas flow of argon gas of 68sccm, reaction gas flow of oxygen gas of 5sccm, deposition temperature of 150 ℃ and deposition pressure of 7.5 × 10-1pa, the sputtering power is 100W, and the deposition time is 0.5-1 h.
3. The preparation of the gel electrolyte and the device packaging of the embodiment are as follows:
(1) adding proper amount of lithium perchlorate (LiClO)4) Vacuum drying at 90 deg.C for 12h to obtain 1.5g LiClO4Mixing the electrolyte with 10g of propylene carbonate and 33.5g of acetonitrile, and stirring for 30-40 min to obtain a transparent electrolyte solution;
(2) adding 4.5g, 4g, 3.5g and 3g of polymethyl methacrylate (PMMA) and 0.5g, 1g, 1.5g and 2g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) into an electrolyte solution, and stirring for 2.5-3.5 h at 65-75 ℃ to obtain a uniformly mixed solution;
(3) will deposit NixOyPutting the film into a container with the surface facing upwards, pouring the mixed solution prepared in the step (2), and performing vacuum drying to ensure that the electrolyte is tightly combined and deposited with NixOyA thin film of conductive glass;
(4) taking out the conductive glass in the step (3) and depositing WO3-xConducting glass of the film is clamped in a staggered mode, vacuum drying is carried out for 2 hours at the temperature of 70 ℃, and an electrochromic device (ECD) is obtained through packaging;
(5) the thickness of the gel electrolyte in the step (3) is 100-200 μm.
FIG. 1 shows WO prepared in example II3-xFilm SEM picture; from FIG. 1, WO prepared in example two3-xThe film has a nano-inclined columnar structure.
FIG. 2 shows Ni prepared in example IIxOyFilm SEM picture; as can be seen from FIG. 2, example II produced NixOyThe film has a nano-inclined columnar structure.
Fig. 3 is a schematic structural diagram of a fast response solid-state thin film type electrochromic device, wherein the edge of the electrochromic device is encapsulated by ultraviolet curing glue.
FIG. 4 shows an ITO/WO with a driving voltage + -5V at a wavelength of 800nm in the third embodiment3-x/PMMA/PVDF-HFP/NixOyThe light modulation amplitude of the ITO electrochromic device; from fig. 4, in the third embodiment, the optical modulation amplitude of the gel electrolyte electrochromic device based on PMMA/PVDF-HFP reaches 30.2% under the conditions of the wavelength of 800nm and the driving voltage ± 5V. From fig. 5, it can be known that in the third embodiment, the gel electrolyte electrochromic device based on PMMA/PVDF-HFP has short response time, the fading response time is 10s, and the coloring response time is 8 s.
FIG. 6 shows ITO/WO3-x/PMMA/PVDF-HFP/NixOya/ITO electrochromic device object diagram.
Claims (9)
1. A preparation method of a PMMA/PVDF-HFP gel electrolyte based fast response electrochromic device is characterized in that the device is a thin film type electrochromic device, has a sandwich structure and comprises a substrate, a transparent conducting layer, an electrochromic layer, an electrolyte layer and an ion storage layer, wherein the electrochromic layer and the ion storage layer are respectively used as a working electrode and a counter electrode of the electrochromic device; the transparent conducting layer is deposited on the substrate, the electrochromic layer and the ion storage layer are respectively deposited on the transparent conducting layer, the electrolyte layer is clamped between the electrochromic layer and the ion storage layer, the electrochromic layer and the ion storage layer are completely coated to form a device, and ultraviolet curing glue is used for packaging the device.
2. The transparent conductive layer according to claim 1, wherein a transparent conductive ITO film is deposited on a rigid transparent glass material by a direct current magnetron sputtering method, and the thickness of the transparent conductive film is 150-200 nm.
3. The electrochromic layer of claim 1 wherein the material is WO with a nanoclinic columnar structure using a glancing angle dc magnetron sputtering process3-xAnd the thin film is deposited on the transparent conducting layer and is tightly combined with the transparent conducting layer to be used as a working electrode, and the thickness of the electrochromic thin film is 420-450 nm.
4. Such as rightThe ion storage layer of claim 1, wherein the ion storage layer is prepared by glancing angle DC magnetron sputtering, and the material is Ni with a nanometer inclined columnar structurexOyAnd the thin film is deposited on the transparent conducting layer and is tightly combined with the transparent conducting layer to be used as a counter electrode, and the thickness of the electrochromic layer ranges from 420 nm to 450 nm.
5. The electrolyte layer according to claim 1, wherein the gel electrolyte is tightly sandwiched between the working electrode and the counter electrode, the ion storage layer of the counter electrode is placed in a container with the ion storage layer facing upward, the liquid electrolyte is poured into the container, the vacuum drying temperature is 60-90 ℃, the vacuum drying time is 8-10 h, so that the electrolyte gel is tightly bonded to the counter electrode, and then the electrolyte gel is interleaved with the electrochromic layer of the working electrode, the vacuum drying temperature is 60-90 ℃, the vacuum drying time is 1-2 h, the working electrode and the counter electrode can be completely coated after the electrolyte is dried, and the electrochromic device (ECD) is obtained by packaging with an ultraviolet curing adhesive under a vacuum condition.
6. Method for the glancing angle direct current magnetron sputtering deposition of an electrochromic layer according to claim 3, characterized in that the deposition temperature is 150 ℃ and the glancing angle is 80oThe deposition pressure is 5 x 10-1pa, the sputtering power is 150W, and the deposition time is 0.5-1.5 h.
7. The method of claim 4 in which the deposition temperature is 150 ℃ and the glancing angle is 80oThe deposition pressure is 7.5X 10-1pa, the sputtering power is 100W, and the deposition time is 0.5-1 h.
8. The method of preparing a gel electrolyte according to claim 5, wherein anhydrous lithium perchlorate (LiClO)4) Dissolving in a mixed solution of propylene carbonate and acetonitrile, stirring to obtain a uniformly mixed transparent electrolyte solution, adding polymethyl methacrylate/polyvinylidene fluoride-hexafluoropropylene (PMMA/PVDF-HFP) into the electrolyte solution, and stirring to obtain the uniformly mixed transparent solution.
9. The polymethyl methacrylate/polyvinylidene fluoride-hexafluoropropylene (PMMA/PVDF-HFP) according to claim 8, wherein the total amount of PMMA/PVDF-HFP is 10wt%, the mass ratio is 9: 1-6: 4, the solution is stirred at the temperature of 65-75 ℃ for 2.5-3.5 h, and the molecular weight of PMMA is 30-60 ten thousand; the polymerization amount of HFP in PVDF-HFP is 20% -30%.
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| CN202110766243.6A CN113433752A (en) | 2021-07-07 | 2021-07-07 | Preparation method of fast response electrochromic device based on PMMA/PVDF-HFP gel electrolyte |
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